Furan polyols

ABSTRACT

This invention relates to novel furan polyols, which are characterized in that they are the product of reaction of a strain selected from the group or consisting of a polyalcohol, a monoamine or polyamine, said polyalcohol or said amine possibly containing a furan cycle and mixtures thereof with a chain extension agent constituted by an organic epoxide, with the proviso that this organic epoxide is a furannic oxiran when this polyalcohol does not contain a furan cycle with the exclusion of 2,5(bis-hydroxy)furan as sole strain, when the chain extension agent does not contain any furan cycle. These furan polyols are used for the preparation of polyurethane foams having improved properties.

The present invention essentially relates to novel furan polyols, to theuse thereof as polyols in the formation of polyurethanes, topolyurethanes thus obtained, and to a process for preparing same.

The flame-retardant properties of the furan cycle owing to theself-extinguishing property of the charring which is formed whencompounds containing a furan cycle are burnt, are already known, cf.U.S. Pat. Nos. 4,029,611, 3,865,757 and 4, 318,999.

In particular, in U.S. Pat. No. 4,318,999, the furan compound isconstituted by 2,5-bis-(hydroxymethyl)furan in combination with ahalogenated polyol to constitute the polyol component made to react withan isocyanate, for the manufacture of rigid polyurethanes with improvedflame resistance. Comparisons are made with furfurylalcohol or withpolyhydroxyfuran as the sole polyol ingredient (tests B and C, Table 1,columns 5 and 6).

Similarly, FR-A-No. 2 536 750 describes novel furan compounds withterminal hydroxy groups, capable of forming active components of rigidcompositions of urethane and of isocyanurate with reducedinflammability. The use of 2,5-bis-(hydroxymethyl) furan (BHMF) isdescribed, of which the chain extension is obtained by propoxylation(page 4, lines 6-12, Examples 1, 2). The use is preferred ofhomopolymers of BHMF (page 4, line 13 to page 9, line 30; Example 3,BHMFP Table III, Example 5, Example 6, claims).

However, it has appeared that the BHMF presents a low reactivity, whichconsiderably limits the use thereof.

Likewise, it has appeared that the mechanical properties of thesepolyurethanes were still unsatisfactory, particularly their dimensionalstability in damp heat as well as an insufficient behavior intemperature.

It is therefore an object of the present invention to solve the newtechnical problem consisting in providing a solution furnishing novelpolyols of the furan type capable of significantly improving thebehaviour of polyurethanes in temperature, their dimensional stabilityin damp heat.

The present invention makes it possible to solve this new technicalproblem for the first time in satisfactory manner.

According to the present invention, novel furan polyols are thusproduced, characterized in that they are the product of reaction of:

(a) a strain selected from the group consisting of a polyalcohol, amonoamine or polyamine, said polyol or said amine possibly containing atleast one furan cycle, and mixtures thereof:

(b) with a chain extension agent, possibly containing at least one furancycle constituted by an organic epoxide, with the proviso that thisorganic epoxide is a furannic oxiran when this strain does not contain afuran cycle; with the exclusion of 2,5-bis-(hydroxymethyl)furan as solestrain, when the chain extension agent does not contain a furan cycle.

According to a particular feature, this amine is a primary or asecondary (mono- or poly-)amine.

According to another feature, this amine can contain one or severalhydroxy functions (groups). When this amine contains at least a hydroxyfunction, preferably at least two hydroxy functions, said hydroxylatedamine can be a tertiary amine. This hydroxylated amine is simultaneouslya polyalcohol of the invention which is aminated.

According to a preferred embodiment, the polyalcohol mentioned aboveresponds to the following chemical formula (I): ##STR1## in which R¹,R², R³ may be identical or different and represent H, a lower alkylgroup with C₁ -C₅, preferably C₁ -C₃, an aliphatic group with alcoholfunction with C₁ -C₄, an aliphatic group with acid function with C₁ -C₄or ester with a lower alkyl ester radical with C₁ -C₅, preferably C₁-C₃, an aliphatic group with ketone function with C₁ -C₄, an aliphaticgroup with aldehyde function with C₁ -C₄ ; n=0 to 10, with the proviso,that, when n=0, at least one of the R¹, R², R³ is a group with alcoholfunction, R¹ not being able to be --CH₂ OH if the chain extension agentdoes not contain a furan cycle; preferably n=1 to 10, and, furtherpreferably n=1 to 3.

The aliphatic groups hereinabove are preferably straight-chain but maybe branched.

According to another preferred feature, R¹ is selected among --H, --CH₂OH with, in that case, n=1 to 10, or --CH₃.

According to another preferred feature, R₂ is selected from ##STR2##with R=H or a lower alkyl group with C₁ -C₅, preferably C₁ -C₃, andpreferably still --CH₃ or --C₂ H5.

According to a particular embodiment, the polyalcohol mentioned above isa furannic polyalcohol corresponding to the following formula: ##STR3##with n=1 to 10, preferably 1 to 3.

According to another variant, the starting polyalcohol is an aliphaticpolyalcohol with C₁ -C₄, preferably selected from ethylene-glycol,propyleneglycol, glycerine, trimethylolpropane, pentaerythritol,sorbitol.

According to another variant, said (mono- or poly-) amine can containone or several hydroxy functions, thereby constituting an aminatedpolyalcohol which can be advantageously obtained by reacting a primaryor secondary(mono- or poly-)amine with a chain extension agentconstituted by the herein defined organic epoxide which can be afurannic epoxide.

According to a particular feature, it can be cited without limitation,as said starting invention amine: NH₃, methylamine, methylenediamine,ethylamine, ethylenediamine, propylamine,1,3-propyldiamine, EDTA, aswell as the corresponding mono- or poly- hydroxylated amines. Apreferred example of hydroxylated amine, or of aminated polyalcohol usedas strain is triethanolamine.

According to yet another particular feature of the invention, theorganic epoxide mentioned above is constituted by propylene oxide.

According to another embodiment of the invention, the organic epoxidementioned above is constituted by a furannic oxiran of formula (II):##STR4## with R¹, R², R³ having the same significance as for thepolyalcohol of formula (I) mentioned above.

And (X) represents either a single carbon-carbon bond or an organicradical, preferably an aliphatic radical, advantageously having from 1to 10 atoms of carbon.

According to another feature of the invention, it also covers the use ofthe above-mentioned furan polyols for constituting a part of all of thepolyols employed in the formation of polyurethanes includingpolyisocyanurates by reaction in particular with isocyanates.

The present invention also covers the polyurethanes, includingpolyisocyanurates, characterized in that they are obtained by reactionof isocyantes with polyols of which at least part is constituted byfuran polyols, such as defined hereinabove. The invention also coversthe process for preparing these furan polyols as defined in the claims.

It has thus been observed that the novel furan polyols according to theinvention make it possible, in completely unexpected manner, to improvethe behavior of the polyurethanes in temperature, their dimensionalstability in damp heat.

The improvement of the properties naturally depends on the proportion ofthese furan polyols according to the invention in the mixture used forpreparing the polyurethanes. It is preferred that the furan polyolsaccording to the invention be the only polyols used in the reaction,although it is possible to use them in combination with other polyols.

The proportion of the incorporation of the polyols according to theinvention may be modified to broad limits. However, it is preferred torespect a number of NCO/number of OH ratio higher than or equal to 1 soas to have an NCO number in excess with respect to the OH number, inparticular to form polyisocyanurates.

All types of polyurethanes or polyisocyanurates, supple or rigid,expanded or not, may naturally be produced with the polyols according tothe invention, whatever their process of production.

Other objects, characteristics and advantages of the invention willappear clearly to the man skilled in the art from the following Examplesgiven simply by way of illustration and in no way limiting the scope ofthe present invention.

EXAMPLE 1

The starting polyalcohol is constituted byacetyl-3-(D-arabinotetroxybutyl) 5-methyl 2-furan of following formula:##STR5##

Reaction is effected with propylene oxide as chain extension agent, theproportion by weight of the propylene oxide relatively to thepolyalcohol mentioned above being 57%, for 6 hours at a temperature of150° C., using 250 ppm of KOH as catalyst.

A furan polyol is thus obtained, having a hydroxyl index equal to 610,determined by the conventional method, and indicating the number of OHfunctions/kg of polyol expressed by weight of KOH.

The functionality of this furan polyol is 4 and its viscosity expressedin centipoises at 20° C. is equal to about 50000.

This furan polyol is used for the preparation of polyurethane foams,bearing reference F₁, in accordance with the following formulation,after having neutralized KOH by tartric acid.

Formulation F₁

Furan polyol hereinabove: 100 parts Surfactant (Sr242® of Schell): 2parts

Catalyst (DMACHA® of BASF): 2 parts

Water: 1 part

Expanding agent (Freon®): 40 parts

Isocyanate MDI: 170 parts

The reaction is carried out in conventional manner and a cream time of13 s is obtained, as well as a filament time of 67 s.

The characteristics of the foam are as follows:

Density (kg/m³): 23

apparent in free expansion λo (mW/m°C): 0.023 λoo (mW/m°C): 0.029

Temperature of the end of degradation of the urethanes (°C.): 320

Loss of weight (%): 26

ΔP%, 400° C.(%): 39 ##EQU1##

EXAMPLE 2

The starting polyalcohol is constituted by 3-(D-arabino-tetroxybutyl)5-methyl 2-furan ethyl acetate of following formula: ##STR6## which isreacted with propylene oxide as chain extension agent, the propyleneoxide representing 52% by weight of the above furan polyalcohol, for 20hrs. at a temperature of 180° C., without catalyst.

A furan polyol is obtained having a hydroxyl index of 570, functionalityof 4, a viscosity in centipoises at 20° C. equal to about 45000.

A formulation of polyurethane foam is made from this furan polyolaccording to the following formulation, referenced F₂ :

Formulation F₂

Polyol mentioned above: 100 parts

Surfactant (Sr242® of Schell): 2 parts

Catalyst (DMCHA® of BASF): 2 parts

H₂ O: 1 part

Expanding agent (Freon®): 40 parts

Isocyanate MDI: 160 parts

By mixing these components, a polyurethane foam is obtained whichpresents a cream time of 20 s and a filament time of 80 s.

The characteristics of this foam are as follows:

Density (kg/m³)

apparent in free expansion: 21

λo (mW/m°C.): 21

Temperature of the end of degradation of the urethanes (°C.): 340

Loss of weight (%): 33

ΔP %, 400° C. (%): 45 ##EQU2##

EXAMPLE 3

The starting polyalcohol is constituted by 3-(D-arabino-tetroxyburyl)5-methyl 2-furan methyl acetate of following formula: ##STR7## which isreacted with propylene oxide as chain extension agent, with a proportionof propylene oxide of 52% by weight, relatively to the above furan, for9 hours at a temperature of 180° C., without catalyst.

A furan polyol is thus obtained having a hydroxyl index equal to 570,functionality of 4, and a viscosity in centipoises at 20° C. equal toabout 45000.

This furan polyol thus obtained is then used for the formulation ofpolyurethane foam according to the following formulation referenced F₃ :

Formulation F₃

Furan polyol: 100parts

Surfactant (Sr242® of Schell): 2 parts

Catalyst (DMCHA® of BASF): 2 parts

H₂ O: 1 part

Expanding agent (Freon®): 40 parts

Isocyanate MDI: 160 parts

With such a formulation, a cream time of 38 s is obtained and a filamenttime of 75 s, and the polyurethane foam obtained presents the followingcharacteristics:

Density (kg/m³)

apparent in free expansion: 22

λo mW/m°C.) : 20

Temperature of the end of degradation of the urethanes (°C.): 320

Loss of weight (%): 38

ΔP %, 400° C. (%): 42.5 ##EQU3##

EXAMPLE 4

The starting polyalcohol is constituted by 2,5-furfuryl dialcohol offollowing formula: ##STR8## which is reacted with furyloxiran as chainextension agent, the proportion of furyloxiran being 64% by weight withrespect to the above-mentioned furfuryl dialcohol, for 48 hours, atambient temperature, without catalyst.

The furan polyol thus obtained presents a hydroxyl index of 250, afunctionality of 2 and a viscosity in centipoises at 20° C. equal toabout 20000.

This furan polyol thus obtained is used for the formulation ofpolyurethane foam, according to the following formulation referenced F₄:

Formulation F₄

Furan polyol hereinabove: 100 parts

Surfactant (Sr242® of Schell): 2 parts

Catalyst (DMCHA® of BASF): 2 parts H₂ O: 1 part

Expanding agent (Freon®): 40 parts

Isocyanate MDI: 79 parts

Non-reactive fluidizing agent: 5 parts

This formulation has an ultra-rapid speed of reaction which does notenable its cream time nor its filament time to be determined.

The characteristics of the polyurethane foam thus obtained are asfollows:

Density (kg/m³)

apparent in free extension: 27 λo (mW/m°C.): 21

Temperature of the end of degradation of the urethanes (°C.): 300

Loss of weight (%): 17

ΔP %, 400° C. (%): 42 ##EQU4##

EXAMPLE 5

The starting polyalcohol is constituted by ethylene glycol as aliphaticpolyalcohol of formula CH₂ OH--CH₂ OH which is reacted with furyloxiranof following formula: ##STR9## the proportion of furyloxiran being 72%by weight with respect to the ethylene glycol, for 24 hrs. and at 55°C., without catalyst.

The furan polyol thus obtained presents a hydroxide index equal to 500,a functionality of 2 and a viscosity in centipoises at 20° C. equal toabout 20000.

The furan polyol thus obtained is used for a formulation of polyurethanefoam referenced F₅, which is as follows:

Formulation F₅

Furan polyol hereinabove: 100 parts

Surfactant (Sr242®) of Schell): 2 parts

Catalyst (DMCHA® of BASF): 2 parts H₂ O: 1 part

Expanding agent (Freon®): 40 parts

Isocyanate MDI: 142 parts

By mixing these components, a polyurethane foam can be prepared, whichpresents a cream time of 15 s and a filament time of 20 s.

The characteristics of this foam thus obtained are as follows:

Density (kg/m³)

apparent in free expansion: 24

λo (mW/m°C.): 20

Temperature of end of degradation of the urethanes (°C.): 300

Loss of weight (%): 21

ΔP%, 400° C. (%): 31 ##EQU5##

Example 6

The starting polyalcohol is constituted by glycerol (aliphaticpolyalcohol of formula CH₂ OH--CHOH--CH₂ OH) which is reacted withfuryloxiran of following formula: ##STR10## as chain extension agent,with a proportion of furyloxiran of 338% by weight, relatively to theglycerol, for 6 hours at room temperature with 0.5% by weight of KOH ascatalyst.

A furan polyol is thus obtained having a hydroxyl index equal to 590, afunctionality of 3.

This furan polyol thus obtained is then used for the formulation ofpolyurethane foam according to the following formulation referenced F₆ :

Formulation F₆

Furan polyol: 100 parts

Surfactant (Sr242® of Schell): 2 parts

Catalyst (DMCHA® of BASF): 2 parts H₂ O: 1 part

Expanding agent (Freon®): 40 parts

Isocyanate MDI: 112 parts

With such a formulation, a cream time of 24 s is obtained and a filamenttime of 39 s, and the polyurethane foam obtained presents the followingcharacteristics:

Density (kg/m³)

apparent in free expansion 27.9

λo mW/m°C.): 21.0

Temperature of the end of degradation of the urethanes (°C.): 340

Loss of weight (%): 24

ΔP %, 400° C. (%): 35 ##EQU6##

EXAMPLE 7 WITH AN AMINE

The starting amine is constituted by triethanolamine of followingformula:

    (HOH.sub.2 C--CH.sub.2).sub.3 N

Triethanolamine is a polyhydroxylated amine and therefore alsoconstitutes a polyalcohol which is aminated.

Triethanolamine is reacted with furyloxiran as chain extension agent,the proportion of furyloxiran being of 220% by weight with respect totriethanolamine i.e. 3 molecules of furyloxiran per triethanolaminemolecule. The reaction occurs without catalyst and begins at about 50°C. while being exothermic.

The furan polyol thus obtained presents a hydroxyl index of 470 with afunctionality of 3.

This furan polyol thus obtained is used for the formulation ofpolyurethane foam, according to the following formulation referenced F₇:

Formulation F₇

Furan polyol hereinabove: 100 parts

Surfactant (Sr242® of Schell): 2 parts

Catalyst (DMCHA® of BASF): 0.5 parts H₂ O: 1 part

Expanding agent (Freon®): 40 parts

Isocyanate MDI: 134 parts

Non-reactive fluidizing agent: 5 parts

This formulation gives a cream time of 35 s. and a filament time of 57s.

The characteristics of the polyurethane foam thus obtained are asfollows:

Density (kg/m³)

apparent in free extension: 28.8

λo (mW/m°C.): 21.7

Temperature of the end of degradation of the urethanes (°C.): 320

Loss of weight (%): 31

ΔP %, 400° C. (%): 41 ##EQU7##

COMPARATIVE EXAMPLE 8

The polyol used is constituted by the non-furannic aminated polyolmarketed by the firm DOW CHEMICAL under reference RA 505, having ahydroxyl index equal to 505, which is a polyol for producing rigidpolyurethane foams with excellent performances.

This comparison polyol is used for the formulation of polyurethane foam,in accordance with the following formulation referenced CF₈ :

Comparison formulation CF₈

Polyol RA 505: 100 parts

Surfactant (Sr242® of Schell): 2 parts

Catalyst (DABCO 33LV® of Air Products): 5 parts

H₂ O: 2 parts

Expanding agent (Freon®): 40 parts

Isocyanate MDI: 143 parts

The reaction of these components makes it possible to obtain apolyurethane foam presenting a cream time of 11 s and a filament time of28 s presenting the following characteristics:

Density (kg/m³) apparent in free expansion: 27.6

λo (mW/m°C.): 17.2

Temperature of end of degradation of the urethanes (°C.): 350

Loss of weight (%): 51

ΔP % 400° C.: 60 ##EQU8##

COMPARATIVE EXAMPLE 9

The comparison polyol used is a conventional polyol marketed by the firmICI under the trade name P130 presenting a mean hydroxyl index of 460,also reputed as producing rigid polyurethane foams giving excellentperformances.

This polyol is used as such for the formulation of polyurethane foamunder the following formulation referenced CF₉ :

Comparison formulation CF₉

Polyol P130 hereinabove: 100 parts

Surfactant (Sr242® of Schell): 2 parts

Catalyst (DABCO 33LV® of Air Products): 5 parts

Expanding agent (Freon®): 40 parts

Isocyanate MDI: 154 parts

The reaction of these components makes it possible to produce apolyurethane foam which presents a cream time of 11 s and a filamenttime of 44 s, having the following characteristics:

Density (kg/m³)

apparent in free expansion: 23.1

λo (mW/m°C.): 0.021

Temperature of end of degradation of the urethanes (°C.): 330

Loss of weight (%) 41; ΔP 400° C. (%): 52.5 ##EQU9##

COMPARATIVE EXAMPLE 10

The comparison example used is a polyol obtained by oxypropylation of2,5-bis-(hydroxy) furan as set forth in FR-A-No. 2536750 (page 17, TableII, sample 2-B-having a measured hydroxyl index of 515. This polyol isused as such for the formulation of a polyurethane foam under thefollowing formulation referenced CF₁₀ :

Comparison formulation CF₁₀

Polyol 2-B Table II of FR-A-No. 2536750: 100 parts

Surfactant (Sr242® of Schell): 2 parts

Catalyst (DABCO 33LV^(R) of Air Products): 5 parts

H₂ O: 2 parts

Expanding agent (Freon® 11): 40 parts

Isocyanate MDI: 162 parts

The reaction of these components makes it possible to produce apolyurethane foam which presents a cream time of 17 s and a filamenttime of 32 s, having the following characteristics:

Density (kg/m³)

apparent in free expansion: 25.3

λo (mW/m°C.): 23.0

Temperature of end of degradation of the urethanes (°C.): 330

Loss of weight (%): 37; ΔP % 400° C. (%): 46 ##EQU10##

It is clearly apparent from the preceding Examples that an unexpectedimprovement is obtained in the properties of the polyurethanes preparedwith the aid of the furan polyols according to the invention.

Comparative Examples 8 to 10 demonstrate this unexpected improvement inthe properties obtained with the furan polyols according to theinvention.

The polyalcohol or amine used may naturally comprise one or more furancycles. According to a particular feature, it is used a hydroxylatedamine which can be in that case a tertiary amine as previously outlined,(among which a preferred example is triethanolamine).

It will be observed that the polyol produced by the reaction accordingto the invention may comprise furan cycles in the chain or pendant fromthis same chain depending on the position and/or the number of thefunctional groups on the furan cycle.

It should be noted that the use of furan epoxide, particularly afurannic oxiran of formula II above said, is very advantageous as it ishighly reactive and avoids the use of a basic catalyst of KOH type whichmust be neutralized subsequently, as the polyols must not be basic,being given that the basicity reduces the reaction with the isocyanates.

As Example 4 demonstrates, no catalyst being used, it may be observedthat, even by carrying out the reaction at ambient temperature, which isa considerable commercial advantage, the duration of the reaction isperfectly acceptable, viz. 48 hrs. In this way, the reaction time isconsiderably reduced by operating at moderate temperature, for exampleabout 50° C.

Thanks to the dimensional stability under hot, damp conditions, they areof considerable interest for tropical countries and even in Europe foroutside use.

It will thus be readily understood that the invention includes all themeans constituting technical equivalents, the means described and theirvarious combinations.

The starting strain (polyalcohol or mono- or poly-)amine) may itself beobtained by reaction of a primary or secondary amine (mono- orpolyamine) with a chain extension agent preferably formed by an organicepoxide which may be a furan epoxide, as herein defined.

In the event of the strain not being a liquid, it may advantageously bepasted with extended polyol or amine before oxylation is effected.

During chain extension, the temperature is regulated to a fixed valueadjustable between ambient temperature and 160° C. depending on thenature of the oxyran and the reactivity of the strain used. A rise intemperature accelerates the speed of reaction without the addition ofbasic catalyst, such as KOH, from about 0 to 250 ppm.

The durations may thus range from some hours to more than 1 day, asdemonstrated in the Examples.

In the description and claims, furan "cycle" is equivalent to furan"ring".

It is also advantageous to use as polyalcohol, the polyalcohols obtainedby the process described in EP No. 0 234 065, preferably thepolyalcohols obtained in examples 1 to 3.

What is claimed is:
 1. A furan polyol comprising the reaction productof:(a) an initiator compound selected from the group consisting of apolyalcohol, a monoamine, a polyamine, and mixtures thereof; and (b) anorganic epoxide chain extension agent, said initiator compoundcontaining at least one furan moiety other than exclusively 2,5bis-(hydroxymethyl)furan moieties when said chain extension agent isfuran moiety free, and said chain extension agent being afuran-containing epoxide when said initiator compound is furan moietyfree.
 2. The furan polyol according to claim 1, wherein said polyalcoholis a C₁ -C₄ aliphatic polyalcohol.
 3. The furan polyol according toclaim 2, wherein said aliphatic polyalcohol is selected from the groupconsisting of ethylene glycol, propylene glycol, glycerine,trimethylolpropane, pentaerythritol and sorbitol.
 4. The furan polyolaccording to claim 1, wherein said amine or polyamine is primary orsecondary and contains at least one hydroxy functionality.
 5. The furanpolyol according to claim 1, wherein said initiator compound is obtainedby the reaction of a mono or polyamine with an epoxide chain extensionagent.
 6. The furan polyol according to claim 1, wherein said organicepoxide chain extension agent is propylene oxide.
 7. The furan polyolaccording to claim 1, wherein said organic epoxide chain extension agentis a furan-containing epoxide.
 8. The furan polyol according to claim 7,wherein said furan-containing epoxide corresponds to the formula:##STR11## wherein R¹, R², and R³ is H, C₁ -C₅ alkyl group, C₁ -C₄aliphatic alcohol group, C₁ -C₄ aliphatic acid group, C₁ -C₅ alkyl estergroup, C₁ -C₄ aliphatic ketone group, C₁ -C₄ aliphatic aldehyde group ormixtures thereof and (X) is an organic radical.
 9. The furan polyolaccording to claim 8, wherein said organic radical is a C₁ -C₁₀aliphatic radical.
 10. A furan polyol comprising the reaction productof(a) a polyalcohol initiator compound, (b) a furan containing epoxidechain extension agent, thereby having pending furan moieties in thefuran polyol reaction product.
 11. A furan polyol comprising onereaction product of:(a) an initiator compound comprising a polyalcohol;and (b) an organic epoxide chain extension agent, said polyalcoholcorresponding to the formula: ##STR12## wherein R¹, R₂, and R₃ is H, C₁-C₅ alkyl group, C₁ -C₄ aliphatic alcohol group, C₁ -C₄ aliphatic acidgroup, C₁ -C₅ alkyl ester group, C₁ -C₄ aliphatic ketone group, C₁ -C₄aliphatic aldehyde group or mixtures thereof; np32 0 to 10, providedthat when n=0, at least one of the R¹, R², R³ is a group with alcoholfunction, R¹ not being able to be CH₂ OH if the chain extension agentdoes not contain a furan cycle.
 12. The furan polyol according to claim11, wherein n is 1 to
 10. 13. The furan polyol according to claim 12,wherein n is 1 to
 3. 14. The furan polyol according to claim 11, whereinR¹ is H, CH₃ or CH₂ OH and when R¹ is CH² OH, n=1 to 10, R² is H, a C₁-C₅ alkyl group, C₁ -C₄ aliphatic alcohol group, C₁ -C₄ aliphatic acidgroup, C₁ -C₅ alkyl ester group, C₁ -C₄ aliphatic ketone group, C₁ -C₄aliphatic aldehyde group or mixtures thereof; and R³ is H or a C¹ -C⁵alkyl group.
 15. The furan polyol according to claim 14, wherein R³ is aC₁ -C₃ alkyl group.
 16. The furan polyol according to claim 15, whereinR³ is CH₃ or C₂ H₅.
 17. The furan polyol according to claim 11, whereinsaid polyalcohol corresponds to the formula: ##STR13## wherein n is 1 to10.
 18. The furan polyol according to claim 11, wherein said organicepoxide chain extension agent is a furan-containing epoxide.
 19. Thefuran polyol according to claim 18, wherein said furan-containingepoxide corresponds to the formula: ##STR14## wherein R¹, R², and R³ isH, C₁ -C₅ alkyl group, C₁ -C₄ aliphatic alcohol group, C₁ -C₄ aliphaticacid group, C₁ -C₅ alkyl ester group, C₁ -C₄ aliphatic ketone group, C₁-C₄ aliphatic aldehyde group or mixtures thereof and (X) is an organicradical.
 20. The furan polyol according to claim 11, wherein saidorganic epoxide chain extension agent is propylene oxide.
 21. A furanpolyol comprising the reaction product of:(a) an initiator compoundcomprising a monoamine or a polyamine; and (b) an organic epoxide chainextension agent, said initiator containing at least one pending furanmoiety when said chain extension agent is furan moiety free and saidchain extension agent being a furan containing epoxide when saidinitiator is furan moiety free, thereby having pending furan moieties inthe furan polyol.
 22. The furan polyol according to claim 21, whereinsaid organic epoxide chain extension agent is propylene oxide.
 23. Thefuran polyol according to claim 21, wherein said organic epoxide chainextension agent is a furan-containing epoxide.
 24. The furan polyolaccording to claim 23, wherein said furan-containing epoxide correspondsto the formula: ##STR15## wherein R¹, R², and R³ is H, C₁ -C₅ alkylgroup, C₁ -C₄ aliphatic alcohol group, C₁ -C₄ aliphatic acid group, C₁-C₅ alkyl ester group, C₁ -C₄ aliphatic ketone group, C₁ -C₄ aliphaticaldehyde group or mixtures thereof and (X) is an organic radical. 25.The furan polyol according to claim 24, wherein said organic radical isa C¹ -C¹⁰ aliphatic radical.
 26. A furan polyol comprising the reactionproduct of:(a) an initiator compound selected from the group consistingof a primary monoamine, a primary polyamine, a secondary monoamine, asecondary polyamine, a hdyroxylated tertiaryamine containing at leasttwo hydroxy functions, (b) a furan-containing organic epoxide chainextension agent thereby having pending furan moieties in the furanpolyol reaction product.
 27. A furan polyol comprising the reactionproduct of(a) an initiator compound comprising an aminated polyalcoholobtained by reacting an amine other than a tertiary amine with afuran-containing epoxide, and (b) an organic epoxide chain extensionagent, thereby having pending furan moieties in the furan polyolreaction product.
 28. A furan polyol comprising the reaction productof:(a) an initiator compound comprising an amine selected from the groupconsisting of NH₃, methylamine, methylenediamine, ethylamine,ethylenediamine, propylamine, 1,3-propyldiamine, EDTA, andtriethanolamine, and (b) a furan-containing epoxy compound therebyhaving pending furan moieties in the furan polyol.
 29. A furan polyolcomprising the reaction product of(a) an initiator compound comprising apolyalcohol corresponding to the formula: ##STR16## wherein R¹, R², andR³ is H, C₁ -C₅ alkyl group, C₁ -C₄ aliphatic alcohol group, C₁ -C₄aliphatic acid group, C₁ -C₅ alkyl ester group, C₁ -C₄ aliphatic ketonegroup, C₁ -C₄ aliphatic aldehyde group or mixtures thereof; n=1 to 10;and (b) an organic epoxide chain extension agent, thereby having pendingfuran moieties in the furan polyol reaction product.
 30. The furanpolyol according to claim 29, wherein n is 1 to
 3. 31. The furan polyolaccording to claim 29, wherein R¹ is H, CH₃ or CH₂ OH, R² is H, a C₁ -C₅alkyl group, C₁ -C₄ aliphatic alcohol group, C₁ -C₄ aliphatic acidgroup, C₁ -C₅ alkyl ester group, C₁ -C₄ aliphatic ketone group, C₁ -C₄aliphatic aldehyde group or mixtures thereof; and R is H or a C¹ -C⁵alkyl group.
 32. The furan polyol according to claim 31, wherein R³ is aC₁ -C₃ alkyl group.
 33. The furan polyol according to claim 32, whereinR³ is CH₃ or C₂ H₅.
 34. A furan polyol comprising the reaction productof:(a) an initiator compound comparing a polyalcohol of formula:##STR17## wherein n is 1 to 10, and (b) an organic epoxide chainextension agent thereby having pending furan moieties the furan reactionproduct.
 35. The furan polyol according to claim 29, wherein saidorganic epoxide chain extension agent is a furan-containing epoxide. 36.The furan polyol according to claim 35, wherein said furan-containingepoxide corresponds to the formula: ##STR18## wherein R¹, R², and R³ isH, C₁ -C₅ alkyl group, C₁ -C₄ aliphatic alcohol group, C₁ -C₄ aliphaticacid group, C₁ -C₅ alkyl ester group, C₁ -C₄ aliphatic ketone group, C₁-C₄ aliphatic aldehyde group or mixtures thereof and (X) is an organicradical.
 37. The furan polyol according to claim 29, wherein saidorganic epoxide chain extension agent is propylene oxide.
 38. A furanpolyol comprising the reaction product of:(a) an initiator compoundselected from the group consisting of a polyalcohol, a monoamine, apolyamine, and mixtures thereof; and (b) an organic epoxide chainextension agent, said epoxide chain extension agent being afuran-containing epoxide, thereby having pending furan moieties in thefuran polyol reaction product.
 39. The furan polyol according to claim38, wherein said polyalcohol is a C₁ -C₄ aliphatic polyalcohol.
 40. Thefuran polyol according to claim 38, wherein said aliphatic polyalcoholis selected from the group consisting of ethylene glycol, propyleneglycol, glycerine, trimethylolpropane, pentaerythritol and sorbitol. 41.The furan polyol according to claim 38, wherein said amine or polyamineis primary or secondary and contains at least one hydroxy functionality.42. The furan polyol according to claim 38, wherein said initiatorcompound is obtained by the reaction of a mono or polyamine with anepoxide chain extension agent.
 43. The furan polyol according to claim38, wherein said furan-containing epoxide corresponds to the formula:##STR19## wherein R¹, R², and R³ is H, C₁ -C₅ alkyl group, C₁ -C₄aliphatic alcohol group, C₁ -C₄ aliphatic acid group, C₁ -C₅ alkyl estergroup, C₁ -C₄ aliphatic ketone group, C₁ -C₄ aliphatic aldehyde group ormixtures thereof and (X) is an organic radical.
 44. The furan polyolaccording to claim 43, wherein said organic radical is a C¹ -C¹⁰aliphatic radical.
 45. A furan polyol comprising the reaction productof:(a) an initiator compound comprising a tertiaryamine being thereaction product of a furan free amine and furannic oxiran, and (b) anorganic epoxide chain extension agent, thereby having pending furanmoieties in the furan polyol.
 46. The furan polyol according to claim45, wherein said organic epoxide chain extension agent is propyleneoxide.
 47. The furan polyol according to claim 45, wherein said organicepoxide chain extension agent is a furan-containing epoxide.
 48. Thefuran polyol according to claim 47, wherein said furan-containingepoxide corresponds to the formula: ##STR20## wherein R¹, R², and R³ isH, C₁ -C₅ alkyl group, C₁ -C₄ aliphatic alcohol group, C₁ -C₄ aliphaticacid group, C₁ -C₅ alkyl ester group, C₁ -C₄ aliphatic ketone group, C₁-C₄ aliphatic aldehyde group or mixtures thereof and (X) is an organicradical.
 49. The furan polyol according to claim 48, wherein saidorganic radical is a C¹ -C¹⁰ aliphatic radical.